CN106279075A - The method that a kind of catalysis 5 Hydroxymethylfurfural prepare 2,5 dimethyl furans - Google Patents
The method that a kind of catalysis 5 Hydroxymethylfurfural prepare 2,5 dimethyl furans Download PDFInfo
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- CN106279075A CN106279075A CN201610668345.3A CN201610668345A CN106279075A CN 106279075 A CN106279075 A CN 106279075A CN 201610668345 A CN201610668345 A CN 201610668345A CN 106279075 A CN106279075 A CN 106279075A
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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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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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
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Abstract
The invention provides the method that a kind of catalysis 5 Hydroxymethylfurfural prepare 2,5 dimethyl furans.The method comprises the following steps: step one, joins in organic solvent by 5 Hydroxymethylfurfural, is configured to 5 Hydroxymethylfurfural solution；Step 2, uses heterogeneous Fe-series catalyst to be catalyzed 5 Hydroxymethylfurfural solution hydrogenation deoxygenations, it is thus achieved that 2,5 dimethyl furans.The heterogeneous Fe-series catalyst catalytically-active metals that the method that the present invention provides uses is ferrum, compares noble ruthenium, palladium and platinum etc. with low cost；Compared with other non-precious metal catalysts, this heterogeneous Fe-series catalyst makes simple, easy to operate, and has higher catalysis activity and selectivity；Use it for being catalyzed 5 Hydroxymethylfurfural (HMF) and prepare 2,5 dimethyl furans (DMF), a kind of method providing high-efficiency environment friendly for the preparation of DMF, and the heterogeneous Fe-series catalyst reclaimed after catalytic reaction can reuse.
Description
Technical field
The invention belongs to organic synthesis technical field, relate to a kind of heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural
(HMF) method preparing 2,5-dimethyl furan (DMF).
Background technology
Along with the continuous minimizing of the fossil resources such as oil, being on the increase of greenhouse gas emissions, and environmental pollution
Day by day serious, using reproducible new forms of energy to substitute traditional fossil energy has become as previous important research direction, Qi Zhongsheng
The material energy as unique regenerative resource containing organic carbon it is considered to be the optimal substitute of fossil energy.
5 hydroxymethyl furfural (HMF), can be hydrolyzed by cellulosic acidic and prepare, be considered as biomass always
One of most important platform chemicals in conversion process.The high functionality of HMF makes it can change into different bio-fuels
Molecule, such as: ethyl levulinate, γ valerolactone, 5-ethoxymethylfurfural, 2,5-dimethyl furans, and value added chemicals, such as: second
Acyl propanoic acid, furfuryl alcohol, 2,5-formylfurans (DMF), 2,5-furan dicarboxylic acid and adipic acid.
DMF is the most attractive in HMF derivant, and it has the premium properties being similar to gasoline, and energy density is high
(30MJ/L), high-octane rating (119), can dissolve each other with gasoline, it is also possible to be used alone, and readily soluble compared with bio-fuel ethanol
Yu Shui, be difficult to preserve, shortcoming that combustibility is low, DMF is considered as a kind of promising biomass fuel.Additionally, DMF
Diels-Alder can also be occurred to react generation bulk chemical xylol with ethylene.
HMF prepares DMF generally by the acquisition of catalyst hydrogenolysis at present.According to the literature, HMF prepares urging of DMF
Agent generally comprises the noble metals such as palladium, ruthenium and platinum, the most also has the report that some base metals such as copper, nickel are catalyzed.Dumesic
Deng using binary system, first fructose selectively dewatering is generated HMF, extract HMF, HMF subsequently at carbon supported copper-ruthenium (CuRu/
C) under the effect of catalyst, hydrogenation deoxidation obtains DMF productivity is 79% (Nature [J], 2007,447,982-986).
Rauchfuss etc. use formic acid to make solvent, and the productivity making fructose obtain DMF by one kettle way under Pd/C catalytic action is 51%
(Angew.Chem.Int.Ed[J],2010,49,6616-6618).Schuth etc. use the catalysis of Pt-Co bimetal nano particles
Agent catalysis HMF prepares DMF, and within 10 minutes, HMF conversion ratio reaches 100%, and after 2 hours, DMF productivity reaches 98% (Nature
Materials[J],2014,13,293-300).Barta etc. use the porous metals oxygen adulterated in supercritical methanol by Cu
The catalyzed conversion HMF of compound, obtains DMF and 2, and 5-dimethyl-tetrahydrofuran (DMTHF) merges productivity and reaches 58%.Subsequently, he
Use Cu0.61, Mg2.33, Al0.98, Ru0.02 and copper-zinc nanometer alloy catalyst, combination (DMF+DMTHF) productivity is high
Reach 97%.CN10355466A discloses a kind of HMF by loading Ni-W on the activated carbon2C catalyst catalyzed conversion, changes into
The selectivity of DMF reaches 96%.
Although the non-precious metal catalyst such as copper, nickel is it has been reported that but still have many problems to need to solve, such as the choosing of DMF
Selecting property is the highest, and non-precious metal catalyst activity is low.
Summary of the invention
In order to promote the development of DMF, improve prior art non-precious metal catalyst and catalyze and synthesize the deficiency of DMF, the present invention
Purpose be to provide a kind of heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural (HMF) to prepare 2,5-dimethyl furan
(DMF) a kind of method, it is intended to develop non-precious metal catalyst utilizing high-efficiency environment friendly and catalyze and synthesize 2,5-dimethyl furan
(DMF) method, promotes the development of DMF.
The purpose of the present invention is achieved by the following technical programs:
The present invention provides a kind of heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural to prepare the side of 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins 5 hydroxymethyl furfural in organic solvent, is configured to 5 hydroxymethyl furfural solution；
Step 2, mixes 5 hydroxymethyl furfural solution and heterogeneous Fe-series catalyst and is placed in enclosed high pressure reactor,
Being re-filled with hydrogen with after hydrogen exchange at least 2 times, under high pressure heated and stirred carries out hydrogenation deoxidation reaction, obtains 2,5-dimethyl
Furan；
Wherein, heterogeneous Fe-series catalyst and 5 hydroxymethyl furfural mol ratio are (1-30): 100.
In above-mentioned preparation method, what hydrogenation deoxidation course of reaction related to reacts the reduction for C=O key and the hydrogen of C-O key
Solve.
In said method, it is preferable that prepare the raw material components of described heterogeneous Fe-series catalyst and include iron compound, nitrogenous
Compound and carrier；
Wherein, in described heterogeneous Fe-series catalyst, in terms of ferrum element, the mass percentage content of ferrum is 2%-10%；
It is further preferred that the mass percentage content of ferrum is 5%.
In said method, the consumption of described nitrogen-containing compound and described carrier carries out Reasonable adjustment according to practical operation.
In said method, it is preferable that described iron compound can be Ferrous acetate.
In said method, it is preferable that described nitrogen-containing compound can include 1,10-phenanthrene quinoline and/or hemin；
It is further preferred that described nitrogen-containing compound is 1,10-phenanthrene quinoline.
In said method, it is preferable that when described nitrogen-containing compound uses hemin, owing to hemin itself contains
Fe, therefore, when nitrogen-containing compound uses hemin, during preparing heterogeneous Fe-series catalyst, can not additional ferrum chemical combination
Thing.
In said method, it is preferable that described carrier can be activated carbon.
In said method, it is preferable that the method preparing described heterogeneous Fe-series catalyst comprises the following steps:
After iron compound, nitrogen-containing compound mixing, add ethanol stirring and dissolving, be subsequently adding carrier reacting by heating, after reaction
Remove ethanol and dry, then pass to hydrogen and calcine under the protection of noble gas, preparing heterogeneous ferrum system and urge
Agent；
Wherein, the temperature of calcining is 400-1000 DEG C；
It is further preferred that the temperature of calcining is 800 DEG C.
In said method, it is preferable that after adding carrier, the temperature of reacting by heating is 60 DEG C, and the response time is 15h.
In said method, it is preferable that described noble gas is argon.
In said method, it is preferable that described organic solvent can include oxolane, normal hexane, methanol, ethanol, positive third
The combination of one or more in alcohol, isopropanol, n-butyl alcohol and sec-butyl alcohol etc.；
It is further preferred that described organic solvent is n-butyl alcohol.
In said method, it is preferable that the consumption of described organic solvent is the 100-of the mole of described 5 hydroxymethyl furfural
1000 times.
In said method, it is preferable that the temperature of hydrogenation deoxidation reaction is 200-280 DEG C, and pressure is 1-5MPa；
It is further preferred that the temperature of hydrogenation deoxidation reaction is 240 DEG C, pressure is 4MPa.
In said method, it is preferable that the method also includes reclaiming heterogeneous Fe-series catalyst for reusing
Step；
It is further preferred that the method reclaiming heterogeneous Fe-series catalyst is: solution reacted to step 2 filter, from
The heart, reclaims heterogeneous Fe-series catalyst.
The present invention provides heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural (HMF) to prepare 2,5-dimethyl furan
(DMF) the heterogeneous Fe-series catalyst catalytically-active metals that method uses is ferrum, compares the low costs such as noble ruthenium, palladium and platinum
Honest and clean；Compared with other non-precious metal catalysts, this heterogeneous Fe-series catalyst makes simple, easy to operate, and has higher
Catalysis activity and selectivity；Using it for being catalyzed 5 hydroxymethyl furfural (HMF) and prepare 2,5-dimethyl furan (DMF), for DMF's
A kind of method that preparation provides high-efficiency environment friendly, and after catalytic reaction, the heterogeneous Fe-series catalyst of recovery can reuse.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, the existing skill to the present invention
Art scheme carries out described further below, but it is not intended that to the present invention can the restriction of practical range.It addition, unless additionally say
Bright, reagent used in following embodiment is the reagent of commercially available analytical pure rank.
Embodiment 1
The present embodiment provides a kind of heterogeneous Fe-series catalyst, and the raw material components preparing this heterogeneous Fe-series catalyst includes
Ferrous acetate, 1,10-phenanthrene quinoline, activated carbon；
Wherein, in above-mentioned heterogeneous Fe-series catalyst, in terms of ferrum element, the mass percentage content of ferrum is 3%.
The present embodiment also provides for the method preparing above-mentioned heterogeneous Fe-series catalyst, and it comprises the following steps:
By Ferrous acetate and 1, the mixing of 10-phenanthrene quinoline adds ethanol and dissolves, and is stirred at room temperature half an hour, is subsequently adding activity
Charcoal is also heated to 60 DEG C of reaction 15h, is then spin-dried for solvent by rotary evaporator, and dries 8h at 60 DEG C with baking oven, then exists
Calcine at a temperature of 800 DEG C under the protection of noble gas, prepare heterogeneous Fe-series catalyst；
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the oxolane of 20mL, is configured to 5-methylol bran
Aldehyde solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is
73.0%, the productivity of product DMF is 32.5%.
Embodiment 2
The present embodiment provides a kind of heterogeneous Fe-series catalyst, and the raw material components preparing this heterogeneous Fe-series catalyst includes
Hemin, activated carbon；
Wherein, in above-mentioned heterogeneous Fe-series catalyst, in terms of ferrum element, the mass percentage content of ferrum is 3%, this enforcement
Example nitrogen-containing compound uses hemin, and itself, containing Fe, therefore prepares the heterogeneous Fe-series catalyst of this group and need not additional
Iron compound.
The present embodiment also provides for the method preparing above-mentioned heterogeneous Fe-series catalyst, and it comprises the following steps:
Hemin adds ethanol dissolve, be stirred at room temperature half an hour, be subsequently adding activated carbon and be heated to 60 DEG C of reactions
15h, is then spin-dried for solvent by rotary evaporator, and dries 8h at 60 DEG C with baking oven, then under the protection of noble gas in
Calcine at a temperature of 800 DEG C, prepare heterogeneous Fe-series catalyst；
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the oxolane of 20mL, is configured to 5-methylol bran
Aldehyde solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is
70.7%, the productivity of product DMF is 30.7%.
Embodiment 3
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the normal hexane of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 45.5%.
Embodiment 4
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the methanol of 20mL, is configured to 5 hydroxymethyl furfural molten
Liquid；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 42.1%.
Embodiment 5
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the ethanol of 20mL, is configured to 5 hydroxymethyl furfural molten
Liquid；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 64.1%.
Embodiment 6
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the normal propyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 69.1%.
Embodiment 7
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the isopropanol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 60.8%.
Embodiment 8
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 75.3%.
Embodiment 9
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the isobutanol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is
99.7%, the productivity of product DMF is 60.9%.
Embodiment 10
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 200 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 64.9%.
Embodiment 11
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 1MPa is carried out to 280 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 78.9%.
Embodiment 12
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 2MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 61.2%.
Embodiment 13
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 3MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 78.6%.
Embodiment 14
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 4MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 83.6%.
Embodiment 15
Prepare heterogeneous Fe-series catalyst with embodiment 1.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 5MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 82.8%.
Embodiment 16
Preparing heterogeneous Fe-series catalyst method with embodiment 1, difference is in the present embodiment, prepares heterogeneous ferrum system and urges
In agent, the mass percentage content of ferrum is 2%.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 4MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 74.1%.
Embodiment 17
Preparing heterogeneous Fe-series catalyst method with embodiment 1, difference is in the present embodiment, prepares heterogeneous ferrum system and urges
In agent, the mass percentage content of ferrum is 5%.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 4MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 86.2%.
Embodiment 18
Preparing heterogeneous Fe-series catalyst method with embodiment 1, difference is in the present embodiment, prepares heterogeneous ferrum system and urges
In agent, the mass percentage content of ferrum is 10%.
The present embodiment also provides for above-mentioned heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural and prepares 2,5-dimethyl furan
Method, it comprises the following steps:
Step one, joins the 5 hydroxymethyl furfural of 0.5mmol in the n-butyl alcohol of 20mL, is configured to 5 hydroxymethyl furfural
Solution；
Step 2, is placed in airtight by the above-mentioned heterogeneous Fe-series catalyst mixing of above-mentioned 5 hydroxymethyl furfural solution and 0.1g
In autoclave, with hydrogen exchange air 3-4 time, being re-filled with hydrogen, the heated under pressure in 4MPa is carried out to 240 DEG C of stirrings
Hydrogenation deoxidation reaction 12h, is detected by gas chromatogram and meteorological chromatograph-mas spectrometer, and the conversion ratio obtaining HMF is 100%,
The productivity of product DMF is 76.2%.
Embodiment 19
After the present embodiment provides the heterogeneous Fe-series catalyst of embodiment 17 to carry out being catalyzed HMF synthesis DMF reaction, carry out back
Receiving recycling, recovery method is the filtration of routine, is centrifuged；Heterogeneous Fe-series catalyst after recovery carries out same embodiment again
The experiment of the catalysis HMF synthesis DMF of 17 same operation.Experimental result is as shown in table 1.
Table 1
From table 1 experimental result, this heterogeneous Fe-series catalyst reuses after reclaiming, and its catalytic effect is steady
Fixed.
In sum, the present invention provides heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural (HMF) to prepare 2,5-diformazan
The heterogeneous Fe-series catalyst catalytically-active metals that the method for base furan (DMF) uses is ferrum, compares noble ruthenium, palladium and platinum etc.
With low cost；Compared with other non-precious metal catalysts, this heterogeneous Fe-series catalyst makes simple, easy to operate, and has
Higher catalysis activity and selectivity；Use it for being catalyzed 5 hydroxymethyl furfural (HMF) and prepare 2,5-dimethyl furan (DMF),
A kind of method providing high-efficiency environment friendly for the preparation of DMF, and after catalytic reaction, the heterogeneous Fe-series catalyst of recovery can weigh
Multiple utilization.
Claims (10)
1. a heterogeneous Fe-series catalyst catalysis 5 hydroxymethyl furfural prepares 2, and the method for 5-dimethyl furan, it includes following
Step:
Step one, joins 5 hydroxymethyl furfural in organic solvent, is configured to 5 hydroxymethyl furfural solution；
Step 2, mixes 5 hydroxymethyl furfural solution and heterogeneous Fe-series catalyst and is placed in enclosed high pressure reactor, use hydrogen
Gas is re-filled with hydrogen after replacing at least 2 times, and under high pressure heated and stirred carries out hydrogenation deoxidation reaction, obtains 2,5-dimethyl furan
Mutter；
Wherein, heterogeneous Fe-series catalyst and 5 hydroxymethyl furfural mol ratio are (1-30): 100.
Method the most according to claim 1, it is characterised in that: prepare the raw material components bag of described heterogeneous Fe-series catalyst
Include iron compound, nitrogen-containing compound and carrier；
Wherein, in described heterogeneous Fe-series catalyst, in terms of ferrum element, the mass percentage content of ferrum is 2%-10%；
Preferably, the mass percentage content of ferrum is 5%.
Method the most according to claim 2, it is characterised in that: described iron compound is Ferrous acetate.
Method the most according to claim 2, it is characterised in that: described nitrogen-containing compound includes 1,10-phenanthrene quinoline and/or blood
Crystalloid；
Preferably, described nitrogen-containing compound is 1,10-phenanthrene quinoline.
Method the most according to claim 2, it is characterised in that: described carrier is activated carbon.
6. according to the method described in any one of claim 1-5, it is characterised in that: prepare the side of described heterogeneous Fe-series catalyst
Method comprises the following steps:
After iron compound, nitrogen-containing compound mixing, add ethanol stirring and dissolving, be subsequently adding carrier reacting by heating, remove after reaction
Ethanol is also dried, and then calcines under the protection of noble gas, prepares heterogeneous Fe-series catalyst；
Wherein, the temperature of calcining is 400-1000 DEG C；
Preferably, the temperature of calcining is 800 DEG C；
Preferably, after adding carrier, the temperature of reacting by heating is 60 DEG C, and the response time is 15h；
Preferably, described noble gas is argon.
Method the most according to claim 1, it is characterised in that: described organic solvent includes oxolane, normal hexane, first
The combination of one or more in alcohol, ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol and sec-butyl alcohol；
Preferably, described organic solvent is n-butyl alcohol.
8. according to the method described in claim 1 or 7, it is characterised in that: the consumption of described organic solvent is described 5-methylol
100-1000 times of the mole of furfural.
Method the most according to claim 1, it is characterised in that: the temperature of hydrogenation deoxidation reaction is 200-280 DEG C, and pressure is
1-5MPa；
Preferably, the temperature of hydrogenation deoxidation reaction is 240 DEG C, and pressure is 4MPa.
Method the most according to claim 1, it is characterised in that: the method also includes carrying out heterogeneous Fe-series catalyst
Reclaim for reusable step；
Preferably, the method reclaiming heterogeneous Fe-series catalyst is: solution reacted to step 2 filters, is centrifuged, and reclaims non-
Homogeneous Fe-series catalyst.
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| CN108940341A (en) * | 2018-07-17 | 2018-12-07 | 中国石油大学(北京) | A kind of catalytic hydrogenation prepares catalyst of alkane and preparation method thereof |
| CN109794244A (en) * | 2019-01-16 | 2019-05-24 | 广州大学 | A kind of copper catalyst and its preparation method and application for 5 hydroxymethyl furfural selective hydrogenation |
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| CN113117706B (en) * | 2019-12-31 | 2024-04-12 | 中国石油化工股份有限公司 | Metal modified ruthenium-based catalyst and method for preparing 2, 5-furan dicarboxylic acid by catalysis of metal modified ruthenium-based catalyst |
| CN113651780A (en) * | 2021-09-27 | 2021-11-16 | 浙江糖能科技有限公司 | Preparation method of 2, 5-tetrahydrofuran dimethanol |
| CN114478445A (en) * | 2022-01-30 | 2022-05-13 | 中国石油大学(北京) | Method for photocatalytic oxidation reforming of biomass-based furan compound |
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