CN108997274A - A kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran - Google Patents
A kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran Download PDFInfo
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- CN108997274A CN108997274A CN201810902104.XA CN201810902104A CN108997274A CN 108997274 A CN108997274 A CN 108997274A CN 201810902104 A CN201810902104 A CN 201810902104A CN 108997274 A CN108997274 A CN 108997274A
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- methylfuran
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 present invention discloses a kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran, belongs to biomass catalyzing transformation technology field.Using the high activity CuZnAl catalyst developed, pass through autoclave stirred reactor, use the molar ratio of furfural and alcohols for 0.1-20mol%, range of reaction temperature is 120 DEG C -240 DEG C, reaction time is 1h-24h, catalyst amount and furfural mass ratio are 0.01-1, can realize the highly selective catalyzed conversion of 2- methylfuran in atmospheric conditions.Without precious metal in catalyst, copper species are mainly by CuO and CuAl2O4Spinel structure composition, and can effectively inhibit the generation of carbon distribution.The advantage that simple process, low production cost, catalyst be environmental-friendly in addition, the present invention has, catalyst is easily isolated, catalyst preparation process is simple, performance is recycled stablizes, and with good economic efficiency and prospects for commercial application.
Description
Technical field
The invention belongs to biomass transformation technology fields, are specifically related to a kind of liquid phase hydrogen migration method, are stirred using autoclave
Reactor efficiently prepares the method for 2- methylfuran by furfural hydrogenation using base metal copper zinc-aluminium material as catalyst.
Background technique
2- methylfuran (MF) is the important industrial chemicals such as production furyl compounds, pentanediol, and as production
The excellent chemical intermediates such as agricultural chemical insecticide (chrysanthemum ethyl ester), perfume, antimalarial (chloroquine).In addition, MF has boiling point lower,
Combustibility preferably feature.Common gasoline is apparently higher than in terms of the performance parameters such as energy density and octane number.Therefore it opens
Hair MF products substitution fossil fuel oil or the additive as current fuel are beneficial to alleviate current energy crisis status, have very
Good historical background and research significance.Increasingly depleted and environmental problem with fossil energy becomes increasingly conspicuous, development and utilization life
The substance energy has been the focus studied in recent years.The wherein furfural biomass plateform molecules important as one kind, mainly from
In raw materials such as corncob, cotton seed hulls, oil tea shell, bagasse.However, the disadvantages such as its property is unstable, utilization rate is low promote us
It is translated into downstream product more effectively with high added value.Although China produces furfural tons up to ten thousand per year, wherein about
80% exports as cheap raw material, therefore seems especially heavy by the downstream product that deep processing is catalytically conveted to high added value
It wants.
Production high valuable chemicals 2- methylfuran is converted for furfural, all there is deficiencies for following known technologies:
Chinese patent, publication number: CN101961652B introduces a kind of copper-chromium-aluminium-Si catalyst for gas phase furfural hydrogenation and prepares 2-
The method of methylfuran, the use temperature of the catalyst are 170-200 DEG C, reaction velocity 0.4-0.6h-1, reaction pressure is
0.001-0.5MPa.Although the selectivity of catalyst furfural conversion ratio and 2- methylfuran with higher, and catalyst uses
It lasts a long time, but uses chromium-based catalysts in reaction process, environmental pollution is serious.
Chinese patent, publication number: CN103028405A introduces a kind of copper oxide-silica composite catalyst for furfural
The method that gas phase hydrogenation prepares 2- methylfuran, reaction temperature section are 60-120 DEG C, reaction pressure 0.05-1MPa.Wherein
For silica mainly as the dispersing agent of active component, the mass percentage of copper oxide (CuO) is 20-80wt%.But in gas
The poor catalyst stability in phase reaction, and corresponding 2- methylfuran yield is lower.
Summary of the invention
The present invention provides the methods that a kind of liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran, with copper zinc-aluminium material
Material is catalyst, in tank reactor, using alcohols as solvent and hydrogen source, in normal pressure and lower temperature (120 DEG C -240 DEG C)
Under the conditions of 2- methylfuran is converted by furfural hydrogenation.It is described using the method for above-mentioned liquid phase hydrogen migration catalytic hydrogenation
CuZnAl catalyst have excellent furfural conversion ratio and 2- methylfuran selectivity.
Technical solution of the present invention:
A kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran, steps are as follows:
Furfural and alcohols mixed solution that molar ratio is 0.1-20mol% are added in reactor, addition passes through in hydrogen
The CuZnAl catalyst of prereduction is crossed, additional air in reactor is discharged, holding reactor pressure is atmospheric pressure, by abundant
It is stirred, reacts 1h-24h under the conditions of 120 DEG C of -240 DEG C of temperature, by separating-purifying up to product 2- methylfuran.
The CuZnAl catalyst dosage and furfural mass ratio is 0.01-1.
The CuZnAl catalyst using coprecipitation method prepare, the Cu content be 10 wt.%-40wt.%,
Zn content is 5wt.%-40wt.%, Al content 40wt.%-60wt.%, and the molar ratio of cu zn is 0.4 or more；Catalysis
Agent chief active is mutually CuAl2O4、CuO、CuAl2O4One of with CuO existing form jointly.
The CuZnAl catalyst prereduction is in H2Under atmosphere, 180 DEG C -350 DEG C of reduction temperature, when reduction a length of 1h-
8h。
The described alcohols mixing is molten not only to have been made solvent has but also done hydrogen source, for methanol, ethyl alcohol, isopropanol, n-butanol, normal propyl alcohol, secondary
The mixing of one or more of butanol.
The reactor is autoclave stirred reactor.
Beneficial effects of the present invention: the present invention provides a kind of are directly catalyzed using liquid phase hydrogen migration method by one step of furfural to turn
Change the technology for preparing 2- methylfuran.It uses alcohols for hydrogen source, does not need to add any acid or basic solvent in reaction process,
Catalyzed conversion is carried out under the conditions of CuZnAl catalyst is existing.It, can be in lower reaction using heretofore described technology
Realized at temperature and normal pressure furfural effective conversion and 2- methylfuran product it is highly selective, and effective slagging prevention is existing
As.Technology of the invention has both green simply, and without being passed through hydrogen in reaction process, and catalyst preparation process is simple, price
Yield that is reasonable and can reaching higher 2- methylfuran, is extremely suitable for being applied to industrial volume production.Method according to the present invention,
In section Example, according to set response parameter, the conversion ratio of furfural selectively may be used up to 95% or more, 2- methylfuran
Up to 70% or more.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of CuZnAl catalyst under different maturing temperatures.
Fig. 2 is X-ray diffraction (XRD) map containing different metal active constituent catalyst.
Fig. 3 is CuZnAl and CuAl sample in H2The characterization result of temperature programmed reduction under atmosphere.
Fig. 4 is X-ray diffraction (XRD) map of different Cu/Zn molar ratio CuZnAl catalysts.
Specific embodiment
Following part combination technology scheme and attached drawing describe a specific embodiment of the invention in detail.
Embodiment 1: the preparation of CuZnAl catalyst.It prepares different metal salt precursor body aqueous solution and uniformly mixes, 60
The mixed solution of sodium carbonate and sodium hydroxide is added dropwise at a temperature of DEG C into the preparation solution, copper zinc-aluminium is obtained using coprecipitation and is urged
Agent.It can control metal ratio in catalyst sample by control metal precursor ratio, prepared not by controlling experiment condition
With the catalyst of metal ratio and copper load capacity.The active phase of catalyst is controlled by control maturing temperature, Fig. 1 display is different
X-ray diffraction (XRD) map of CuZnAl catalyst under maturing temperature.The copper zinc-aluminium containing hydrotalcite precursor is measured through experiment to urge
Agent contains active phase CuAl after roasting2O4Phase and CuO phase, the two form synergistic effect, can be realized higher furfural conversion
The yield of rate and 2- methylfuran.
Embodiment 2: after roasting 3h at catalyst series in air 600 DEG C, at 280 DEG C, H2Reduction treatment under atmosphere
After 3h, pour into the furfural equipped with 0.3mol% and isopropanol reaction kettle.Using mixing speed 800rpm, when reaction a length of 4h,
Reaction temperature is 180 DEG C, and pressure is X-ray diffraction (XRD) figure that 0.1MPa. Fig. 2 is different component catalyst sample before reacting
Spectrum, Fig. 3 show CuZnAl and CuAl typical sample in H2The characterization result of temperature programmed reduction under atmosphere.The following table 2 is shown in that difference is urged
Agent is catalyzed the result that furfural hydrogenation prepares 2- methylfuran by liquid phase hydrogen migration.
Table 2
aOther liquid products that not can determine that its composition.
Embodiment 3: being the CuZnAl catalyst that 2.5, Al accounts for 49mol% with Cu/Zn molar ratio, by 600 DEG C of air
After roasting 3h, in H2Reduction pretreatment 3h at 280 DEG C in atmosphere pours into furfural and isopropanol reaction kettle equipped with 0.3mol%
In, mixing speed 800rpm, when reaction a length of 4h.The following table 3 adds liquid phase hydrogen migration catalysis furfural under the conditions of seeing differential responses
Hydrogen prepares the result of 2- methylfuran.
Table 3
Embodiment 4: being the CuZnAl catalyst that 2.5, Al accounts for 49mol% with Cu/Zn molar ratio, by 600 DEG C of air
After roasting 3h, in H2Reduction pretreatment 3h at 280 DEG C in atmosphere pours into furfural equipped with 0.3mol% and ethyl alcohol, normal propyl alcohol, different
Propyl alcohol, n-butanol, in sec-butyl alcohol reaction kettle.Reaction condition are as follows: load catalyst 0.15g, 180 DEG C of reaction temperature, mixing speed
For 800rpm, when reaction a length of 4h.The following table 4 is shown in solvent to liquid phase hydrogen migration catalysis furfural selective hydrogenation preparation 2- methyl furan
The result muttered.
Table 4
Embodiment 5: being respectively 0.5:1,1.0:1,1.5:1,2.0:1,2.5:1,3.0:1,3.5 with Cu/Zn molar ratio:
1,4.5:1, Al account for the CuZnAl catalyst of 49mol%, after roasting 3h in 600 DEG C of air, in H2In atmosphere at 280 DEG C also
Original pretreatment 3h, is poured into the furfural equipped with 0.3mol% and isopropanol reaction kettle, mixing speed 800rpm, and when reaction is a length of
4h, pressure is 0.1MPa before reacting.Fig. 3 shows X-ray diffraction (XRD) figure of CuZnAl catalyst under different Cu/Zn molar ratios
Spectrum.The following table 5 is shown in that the CuZnAl catalyst of different Cu/Zn molar ratios is catalyzed furfural hydrogenation by liquid phase hydrogen migration and produces 2- methyl
The result of furans.
Table 5
Embodiment 6: it is the CuZnAl catalyst that 2.5, Al accounts for 49mol% with Cu/Zn molar ratio, which is existed respectively
With 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C in air atmosphere, 800 DEG C of roasting temperature 3h, then by above-mentioned catalyst in H2Gas
Reduction pretreatment 3h at 280 DEG C in atmosphere is poured into the furfural equipped with 0.3mol% and isopropanol reaction kettle, mixing speed
800rpm, when reaction a length of 4h, pressure is 0.1 MPa before reacting.Fig. 4 is that the X of CuZnAl catalyst under different maturing temperatures is penetrated
Line diffraction (XRD) map.The CuZnAl catalyst that the following table 6 is shown under different maturing temperatures is catalyzed furfural by liquid phase hydrogen migration and adds
The result of hydrogen production 2- methylfuran.
Table 6
Embodiment 7: being the CuZnAl catalyst that 2.5, Al accounts for 49mol% with Cu/Zn molar ratio, by 600 DEG C of air
After roasting 3h, in H2Reduction pretreatment 3h at 280 DEG C in atmosphere pours into furfural and isopropanol reaction kettle equipped with 0.3mol%
In, the reaction time is respectively 1h, 2h, 3h, 4h, 5h.800 rpm of mixing speed, pressure is 0.1MPa before reacting.The following table 7 is shown in not
With under reaction duration, liquid phase hydrogen migration is catalyzed the result of furfural hydrogenation production 2- methylfuran.
Table 7
Embodiment 8: being the CuZnAl catalyst that 2.5, Al accounts for 49mol% with Cu/Zn molar ratio, by 600 DEG C of air
After roasting 3h, in H2Reduction pretreatment 3h at 280 DEG C in atmosphere pours into furfural and isopropanol reaction kettle equipped with 0.3mol%
In, reaction time 4h, pressure is 0.1MPa before reacting.Catalyst passes through 5 circular responses.The following table 8 is shown in 5 circular response mistakes
Cheng Zhong, liquid phase hydrogen migration are catalyzed the result of furfural hydrogenation production 2- methylfuran.
Table 8
Describe the present invention and its several embodiments by way of example rather than limitation above.The common skill of this field
Art personnel can associate other alternative embodiments after reading this specification, these embodiments are also of the invention
Within the scope of.
Claims (10)
1. a kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran, which is characterized in that steps are as follows:
Furfural and alcohols mixed solution that molar ratio is 0.1-20mol% are added in reactor, are added in hydrogen by pre-
Additional air in reactor is discharged in the CuZnAl catalyst of reduction, and holding reactor pressure is atmospheric pressure, by being sufficiently stirred
Mixing, reacts 1h-24h under the conditions of 120 DEG C of -240 DEG C of temperature, by separating-purifying up to product 2- methylfuran.
2. the method that liquid phase hydrogen migration catalysis furfural hydrogenation according to claim 1 prepares 2- methylfuran, feature exist
In the CuZnAl catalyst is prepared using coprecipitation method, and the Cu content is 10wt.%-40wt.%, Zn content
For 5wt.%-40wt.%, Al content 40wt.%-60wt.%, and the molar ratio of cu zn is 0.4 or more；Catalyst is main
Active is mutually CuAl2O4、CuO、CuAl2O4One of with CuO existing form jointly.
3. the method that liquid phase hydrogen migration catalysis furfural hydrogenation according to claim 1 or 2 prepares 2- methylfuran, feature
It is, the CuZnAl catalyst dosage and furfural mass ratio are 0.01-1.
4. the method that liquid phase hydrogen migration catalysis furfural hydrogenation according to claim 1 or 2 prepares 2- methylfuran, feature
It is, the CuZnAl catalyst prereduction is in H2Under atmosphere, 180 DEG C -350 DEG C of reduction temperature, when reduction a length of 1h-8h.
5. the method that liquid phase hydrogen migration catalysis furfural hydrogenation according to claim 3 prepares 2- methylfuran, feature exist
In the CuZnAl catalyst prereduction is in H2Under atmosphere, 180 DEG C -350 DEG C of reduction temperature, when reduction a length of 1h-8h.
6. the according to claim 1, method that the catalysis of liquid phase hydrogen migration described in 2 or 5 furfural hydrogenation prepares 2- methylfuran, special
Sign is that it is methanol, ethyl alcohol, isopropanol, n-butanol, normal propyl alcohol, Zhong Ding that the alcohols mixing is molten, which not only to have been made solvent but also done hydrogen source,
The mixing of one or more of alcohol.
7. the method that liquid phase hydrogen migration catalysis furfural hydrogenation according to claim 3 prepares 2- methylfuran, feature exist
In the alcohols mixing is molten not only to have been made solvent but also done hydrogen source, in methanol, ethyl alcohol, isopropanol, n-butanol, normal propyl alcohol, sec-butyl alcohol
One or more kinds of mixing.
8. the method that liquid phase hydrogen migration catalysis furfural hydrogenation according to claim 4 prepares 2- methylfuran, feature exist
In the alcohols mixing is molten not only to have been made solvent but also done hydrogen source, in methanol, ethyl alcohol, isopropanol, n-butanol, normal propyl alcohol, sec-butyl alcohol
One or more kinds of mixing.
9. the according to claim 1, method that the catalysis of liquid phase hydrogen migration described in 2,5,7 or 8 furfural hydrogenation prepares 2- methylfuran,
It is characterized in that, the reactor is autoclave stirred reactor.
10. the method that liquid phase hydrogen migration catalysis furfural hydrogenation according to claim 6 prepares 2- methylfuran, feature exist
In the reactor is autoclave stirred reactor.
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Cited By (5)
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| CN109796428A (en) * | 2019-03-28 | 2019-05-24 | 北京化工大学 | A kind of copper-based catalysts add the application in hydrogen in 5 hydroxymethyl furfural |
| CN112892537A (en) * | 2021-01-25 | 2021-06-04 | 大连理工大学 | Preparation method and application of easily-recycled high-selectivity furfural hydrogenation catalyst |
| CN114573528A (en) * | 2022-03-23 | 2022-06-03 | 华北电力大学 | Method for preparing organic alcohol by reducing organic aldehyde compound through catalytic ethanol |
| CN115446301A (en) * | 2021-05-21 | 2022-12-09 | 中国科学院大连化学物理研究所 | Copper nanoparticle material and preparation and application thereof |
| CN115746325A (en) * | 2022-11-25 | 2023-03-07 | 山西大学 | Construction method of biosensor based on nanogold-metal organic framework material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115446301A (en) * | 2021-05-21 | 2022-12-09 | 中国科学院大连化学物理研究所 | Copper nanoparticle material and preparation and application thereof |
| CN114573528A (en) * | 2022-03-23 | 2022-06-03 | 华北电力大学 | Method for preparing organic alcohol by reducing organic aldehyde compound through catalytic ethanol |
| CN115746325A (en) * | 2022-11-25 | 2023-03-07 | 山西大学 | Construction method of biosensor based on nanogold-metal organic framework material |
| CN115746325B (en) * | 2022-11-25 | 2023-09-22 | 山西大学 | Biosensor construction method based on nano gold-metal organic framework material |
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