CN109776463A - The preparation method of 2,5- furandicarboxylic acid dialkyl ester - Google Patents
The preparation method of 2,5- furandicarboxylic acid dialkyl ester Download PDFInfo
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Abstract
Contain 5-membered ring compounds technical field of 1 oxygen atom as only heteroatom the invention belongs to the thick sum of other rings of getting along well, more particularly to 2, the preparation method of 5- furandicarboxylic acid dialkyl ester, comprising the following steps: furfuraldehyde through catalytic oxidation is furancarboxylic acid using copper oxide as catalyst by A.；B. furancarboxylic acid, carbonate, ionic liquid and alcohol are sequentially introduced into autoclave, closed, nitrogen purges 3 times, is filled with carbon dioxide to 1-4MPa, reaction temperature is 100-150 DEG C, reaction time 6-24h；The ionic liquid is -3 methylimidazole tetrafluoro boric acid of 1- butyl, -3 methylimidazole hexafluorophosphoric acid of 1- butyl, -3 methylimidazole nitric acid of 1- butyl, -3 methylimidazole tetrafluoro boric acid of 1- ethyl diethyldithiocarbamate ether, -3 methylimidazole hexafluorophosphoric acid of 1- ethyl diethyldithiocarbamate ether, -3 methylimidazole hexafluorophosphoric acid of 1- ethyl-methyl ether, -3 methylimidazole nitric acid of -3 methylimidazole tetrafluoro boric acid of 1- nitrile propyl, -3 methylimidazole hexafluorophosphoric acid of 1- nitrile propyl or 1- nitrile propyl.This method reaction condition is relatively mild, catalytic activity and reaction selectivity are high.
Description
Technical field
Contain five-membered ring chemical combination of 1 oxygen atom as only heteroatom the invention belongs to the thick sum of other rings of getting along well
A kind of object technical field, and in particular to preparation method of 2,5-furandicarboxylic acid dialkyl ester.
Background technique
As industrialization degree is further deepened, CO2 emissions are sharply increased, so that global warming, ecology
Environmental disruption, Melting Glacierss, sea level rise, storm tide increase, crop yield decline, Dry land, the increasing of desertification area
Greatly, the natural calamities such as tsunami earthquake, extremely hot severe cold take place frequently, and seriously endanger the living environment to the mankind and healthy and safe (" low-carbon-
The inevitable choice of human survival ", Meng Xiangfu etc., chemistry world, the 2nd phase of volume 52 in 2011, the 127-128 pages, publication date
On 04 27th, 2011；" China Exports research under low-carbon economy background ", Wang Bing, University of Anhui's master thesis,
2013, abstract, publication date on December 31st, 2013).In December, 1997, the representative of 149 countries and regions is in kyoto, Japan
In the 3rd meeting of the United Nations Framework Convention on Climate Change held, the negotiation difficult by anxiety, meeting, which has passed through, to be intended to
Developed country's greenhouse gas emissions are limited in the hope of inhibiting the Kyoto Protocol of global warming.
Currently, reduce CO2 emissions approach mainly have following three: (1) tap a new source of energy, reduce fossil and
The fuel of biomass；(2) collecting carbonic anhydride and geological storage is carried out；(3) chemical utilization of carbon dioxide.
However, new energy can not also substitute fossil feedstock in a short time, although the geological storage of carbon dioxide can be a large amount of
Carbon emission is reduced, but consequent effects need to study.Therefore, the chemical conversion of carbon dioxide will reduce CO2 emission
One important channel of amount.Fix the synthesis for also there was only urea of carbon dioxide on a large scale with the fixed method of chemistry.Currently, related
In by adding relevant report of the hydrogen by carbon dioxide conversion for formic acid, methanol, methane etc..However, the confession of hydrogen should belong at present
Fine chemicals (" Technique of Manufacturing Alkene from Natural Gas brief introduction ", Hu original etc., oil-gas field surface engineering, the 8th phase of volume 25 in 2006, the
Page 66, publication date on December 31st, 2006), and activate carbon dioxide and then often require to use unsaturated compound, small molecule
Cyclic compound and the substances such as organo-metallic compound.Therefore, by add hydrogen by carbon dioxide conversion be formic acid, methanol,
Methane is still within the laboratory research stage, cannot achieve industrialized production.
Biomass is a kind of important renewable energy, is the carrier of hydrogen, compared with fossil fuel, has volatility height,
Sulphur, nitrogen content are low, renewable, low pollution, it is widely distributed the features such as (" application and research of gasification of biomass ", Zhao Lianchen etc. can
The renewable sources of energy, the 6th phase of volume 26 in 2008, the 55-58 pages, publication date on December 31st, 2008；" biomass thermal chemical conversion system
Hydrogen technology ", Yan Guihuan etc., renewable energy, the 4th phase in 2004, the 33-36 pages, publication date on December 31st, 2004).In addition,
Biomass rich content on earth, it is cheap and can be good at realizing carbon cycle, as a kind of sustainable and renewable
Resource has very big potentiality in terms of replacing traditional oil product, can be good at meeting society to fuels and chemicals
Demand, to realize transition from from non-renewable petroleum resources to renewable energy.The main component of plant biolobic material
It is carbohydrate i.e. cellulose and lignin, is decomposed into corresponding monomer under certain condition, wherein hexose and pentose (packet
Include glucose, fructose and xylose) it is the most common component units.Furan derivative is one kind weight being transformed by glucose
The platform chemicals wanted, these furan derivatives mainly include 2,5-furandicarboxylic acid etc..These furan derivatives are not only
The alternative chemicals generated by crude oil can be used as raw material for synthesizing new compound, such as ambroin acid, 2,5-
(" furans platform chemicals are urged for dimethylamino tetrahydrofuran, 2,5- dihydroxytetrahydrofandn, polyamide, polyester and polyurethane etc.
Change is converted into renewable chemicals and dyestuff ", Zhao Rongrong etc., Journal of Molecular Catalysis, the 5th phase of volume 28 in 2014, the 485-95 pages, public affairs
Open on October 2014 day 31；" engineering large intestine Orange Producing high added value organic acid, alcohol progress ", Wang Jiming etc., biology
Engineering journal, the 10th phase of volume 29 in 2013, the 1363-1373 pages, publication date on October 25th, 2013).
It is well known that currently, 2,5-furandicarboxylic acid mainly by 5 hydroxymethyl furfural oxidation from, 2,5-furandicarboxylic acid
Dialkyl ester is mainly esterified by 2,5-furandicarboxylic acid come still, 2,5-furandicarboxylic acid is limited to 5- methylol chaff
The amount of aldehyde cannot achieve large-scale production.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of, 2,5-furandicarboxylic acid dialkyl ester preparation method, it should
Method reaction condition is relatively mild, and catalytic activity and reaction selectivity are high, and the reaction time is relatively short.
To achieve the above object, the technical solution of the present invention is as follows:
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, comprising the following steps:
It A. is furancarboxylic acid by furfuraldehyde through catalytic oxidation using copper oxide as catalyst；
B. it synthesizes 2,5- furandicarboxylic acid dialkyl ester: furancarboxylic acid, carbonate, ionic liquid and alcohol is sequentially introduced into high pressure
Closed in reaction kettle, nitrogen purges 3 times, is filled with carbon dioxide to 1-4MPa, and reaction temperature is 100-150 DEG C, and the reaction time is
6-24h；The ionic liquid is -3 methylimidazole tetrafluoro boric acid of 1- butyl, -3 methylimidazole hexafluorophosphoric acid of 1- butyl, 1- butyl -
3 methylimidazole nitric acid, -3 methylimidazole tetrafluoro boric acid of 1- ethyl diethyldithiocarbamate ether, -3 methylimidazole hexafluorophosphoric acid of 1- ethyl diethyldithiocarbamate ether,
- 3 methylimidazole hexafluorophosphoric acid of 1- ethyl-methyl ether, -3 methylimidazole tetrafluoro boric acid of 1- nitrile propyl, -3 methylimidazole of 1- nitrile propyl
- 3 methylimidazole nitric acid of hexafluorophosphoric acid or 1- nitrile propyl.
Further, the mass ratio of the copper oxide and furfural is 0.1:1-0.3:1.
Further, in step A, the reaction condition of the catalysis oxidation are as follows: nitrogen purges 3 times, fills air or oxygen extremely
0.1-3MPa, reaction temperature are 30-60 DEG C, reaction time 4-6h.
Further, the carbonate is sodium carbonate, potassium carbonate, cesium carbonate or rubidium carbonate.
Further, the mass ratio of the carbonate and furancarboxylic acid is 0.1:1-0.3:1.
Further, the mass ratio of the ionic liquid and furancarboxylic acid is 10:1-20:1.
Further, the alcohol is methanol, ethyl alcohol, propyl alcohol or butanol.
Further, the molar ratio of the alcohol and furancarboxylic acid is 2:1-10:1.
Further, the preparation method of the 2,5-furandicarboxylic acid dialkyl ester, comprising the following steps:
A. catalysis oxidation furfural is furancarboxylic acid:
Furfural and copper oxide are sequentially introduced into autoclave, closed, nitrogen purges 3 times, fills air or oxygen extremely
0.1-3MPa, reaction temperature are 30-60 DEG C, reaction time 4-6h, and Filtration of catalyst, acidification of filtrate to pH is 3-2.5,
Suction strainer, washing, drying, drying temperature are 80-120 DEG C, drying time 2-4h；The catalyst is to the mass ratio of furfural
0.1:1-0.3:1；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized
Furancarboxylic acid, carbonate, ionic liquid and alcohol are sequentially introduced into autoclave, closed, nitrogen purges 3 times, fills
Carbon dioxide is to 1-4MPa, and reaction temperature is 100-150 DEG C, and organic solvent is added in reaction time 6-12h after completion of the reaction,
Filtering recycles ionic liquid and catalyst, organic solvent is distilled to recover to obtain 2,5 furandicarboxylic acid dialkyl esters；It is used
Alcohol be methanol, ethyl alcohol, propyl alcohol or butanol；The carbonate is sodium carbonate, potassium carbonate, cesium carbonate or rubidium carbonate；The ion
Liquid be -3 methylimidazole tetrafluoro boric acid of 1- butyl, -3 methylimidazole hexafluorophosphoric acid of 1- butyl, -3 methylimidazole nitric acid of 1- butyl,
- 3 methylimidazole tetrafluoro boric acid of 1- ethyl diethyldithiocarbamate ether, -3 methylimidazole hexafluorophosphoric acid of 1- ethyl diethyldithiocarbamate ether, 1- ethyl-methyl ether -3
Methylimidazole hexafluorophosphoric acid, -3 methylimidazole tetrafluoro boric acid of 1- nitrile propyl, -3 methylimidazole hexafluorophosphoric acid of 1- nitrile propyl or 1- nitrile
The mass ratio of -3 methylimidazole nitric acid of propyl, the carbonate and furancarboxylic acid is 0.1:1-0.3:1, and the molar ratio of alcohol and furancarboxylic acid is 2:
The mass ratio of 1-10:1, ionic liquid and furfural is 10:1-20:1.
Further, the organic solvent is ethyl acetate or ether.
The beneficial effects of the present invention are:
Raw material sources used by method of the invention are abundant, can obtain on a large scale.
Method reaction condition of the invention is relatively mild, can get the yield of the furandicarboxylic acid dialkyl ester of 91-97%
It is relatively short with the conversion ratio of 100% furfural, reaction time.
Method catalyst of the invention and reaction system may be reused 10 times or more, 2,5- furans two convenient for separation
The yield of formic acid dialkyl ester is still up to 93%-97%.
Specific embodiment
Illustrated embodiment is to preferably be illustrated to the contents of the present invention, but is not that the contents of the present invention only limit
In illustrated embodiment.So those skilled in the art carry out nonessential change to embodiment according to foregoing invention content
Into and adjustment, still fall within protection scope of the present invention.
The detection method of the conversion ratio of following furfural are as follows: furfural content, flowing are detected using liquid chromatogram UV detector
It is mutually that the sulfuric acid of (20%) 5mmol/L and the chromatography methanol of (80%) form, pillar is C18 reversed-phase column, flow velocity 0.6ml/
Min, Detection wavelength 280nm (react starting to add with 0.10% (react starting and furfural amount is added, % is mass fraction), 30%
Enter furfural amount, % is mass fraction), 50% (reaction starting be added furfural amount, % is mass fraction), 70% (reaction starting plus
Enter furfural amount, % is mass fraction), 90% (reaction starting be added furfural amount, % is mass fraction) and 100% (reaction originate
Furfural amount is added, % is mass fraction) furfural make external standard curve (external standard method), the standard curve of production is straight line, with chaff
The concentration of aldehyde is abscissa, and the area of chromatographic peak is ordinate；The chromatographic peak area for the furfural that liquid assay goes out after reaction is corresponding
In the concentration of furfural on standard curve, unreacted chaff can be calculated multiplied by the volume of liquid after obtained reaction with the concentration
The quality of aldehyde, then according to formulaThe conversion of furfural is calculated
Rate；
The test method of the yield of following 2,5- furandicarboxylic acid dialkyl ester are as follows: use liquid chromatogram differential pulse polarograpll
Device carries out the content of detection 2,5-furandicarboxylic acid dialkyl ester, and mobile phase is the aqueous sulfuric acid of 5mmol/L, pillar HPX-
87H column, flow velocity 0.6ml/min, with 0.10%, (reaction starting is added furfural and is fully converted to 2,5-furandicarboxylic acid dialkyl group
Ester, % are mass fraction), 30% (reacts starting addition furfural and is fully converted to 2,5-furandicarboxylic acid dialkyl ester, % is matter
Amount score), 50% (reaction starting be added furfural be fully converted to 2,5-furandicarboxylic acid dialkyl ester, % is mass fraction),
70% (reaction starting is added furfural and is fully converted to 2,5-furandicarboxylic acid dialkyl ester, and % is mass fraction), 90% (reaction
Starting be added furfural be fully converted to 2,5-furandicarboxylic acid dialkyl ester, % is mass fraction) and 100% (reaction starting add
Enter furfural and be fully converted to 2,5-furandicarboxylic acid dialkyl ester, % is mass fraction) 2,5-furandicarboxylic acid dialkyl ester
It makes external standard curve (external standard method), the standard curve of production is straight line, is cross with the concentration of 2,5-furandicarboxylic acid dialkyl ester
Coordinate, the area of chromatographic peak are ordinate.The chromatographic peak area pair for the furandicarboxylic acid dialkyl ester that liquid assay goes out after reaction
It should be in the concentration of furandicarboxylic acid dialkyl ester on standard curve, with the concentration multiplied by the volume of liquid after obtained reaction
The quality for calculating furans 2,5-furandicarboxylic acid dialkyl ester, then according to formulaThe yield of 2,5- furandicarboxylic acid dialkyl ester is calculated.
Embodiment 1
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 3g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
0.1MPa, reaction temperature are 30 DEG C, reaction time 3h, Filtration of catalyst, and it is 2.5 that filtrate, which is acidified to pH with sulfuric acid, are inhaled
Filter, washing dry 4h at 80 DEG C to get furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 3g potassium carbonate, -3 methylimidazole hexafluorophosphoric acid of 200g ionic liquid 1- butyl, 11ml ethyl alcohol is successively
It is introduced into autoclave, closed, nitrogen purges 3 times, filling CO 2 to 1MPa, and reaction temperature is 100 DEG C, the reaction time
For 6h, 100ml anhydrous ether is added after completion of the reaction, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether, mistake
Filter, is recovered to -3 methylimidazole hexafluorophosphate of 1- butyl and potassium carbonate, anhydrous ether is distilled to recover, 2,5- furans two is obtained
Formic acid dialkyl ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 93%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole hexafluorophosphoric acid of ionic liquid 1- butyl according to this implementation
Example the method is reused 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester according to the present embodiment the method, furfural
Conversion ratio is 100%, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 93%.
Embodiment 2
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 1g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
3MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 3 that filtrate, which is acidified to pH with sulfuric acid, suction strainer, water
It washes, dry 2h at 12 DEG C to get furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 1g sodium carbonate, -3 methylimidazole tetrafluoro boric acid of 100g ionic liquid 1- butyl, 8ml methanol successively draws
Enter into autoclave, closed, nitrogen purges 3 times, filling CO 2 to 4MPa, and reaction temperature is 150 DEG C, and the reaction time is
100ml ethyl acetate is added after completion of the reaction, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether, mistake by 12h
Filter, is recovered to -3 methylimidazole tetrafluoro boric acid of 1- butyl and sodium carbonate, ethyl acetate is distilled to recover, obtain 2,5- furans diformazan
Acid dialkyl ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 91%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole tetrafluoro boric acid of ionic liquid 1- butyl according to this implementation
Example the method is reused 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester according to the present embodiment the method, furfural
Conversion ratio is 100%, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 91%.
Embodiment 3
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 2g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
1MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 2.8 that filtrate, which is acidified to pH with sulfuric acid, suction strainer,
3h is dried in washing at 100 DEG C, has obtained furancarboxylic acid both up to furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 1g rubidium carbonate, -3 methylimidazole nitric acid of 150g ionic liquid 1- butyl, 67ml normal propyl alcohol successively draws
Enter into autoclave, closed, nitrogen purges 3 times, filling CO 2 to 3MPa, and reaction temperature is 120 DEG C, and the reaction time is
100ml ethyl acetate is added after completion of the reaction, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether by 8h, filters,
It is recovered to -3 methylimidazole nitric acid of 1- butyl and rubidium carbonate, ethyl acetate is distilled to recover, obtains 2,5 furandicarboxylic acid dialkyl group
Ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 90%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole nitric acid of ionic liquid 1- butyl according to the present embodiment institute
It states method to reuse 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester, the conversion of furfural according to the present embodiment the method
Rate is 100%, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 90%.
Embodiment 4
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 2g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
1MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 2.8 that filtrate, which is acidified to pH with sulfuric acid, suction strainer,
4h is dried in washing at 80 DEG C, both obtains furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 1g rubidium carbonate, -3 methylimidazole tetrafluoro boric acid of 150g ionic liquid 1- ethyl diethyldithiocarbamate ether, 30ml is just
Butanol is sequentially introduced into autoclave, closed, and nitrogen purges 3 times, filling CO 2 to 1MPa, and reaction temperature is 120 DEG C,
Reaction time is 8h, and 100ml ethyl acetate is added after completion of the reaction, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous second
In ether, filtering is recovered to -3 methylimidazole hexafluorophosphoric acid of 1- butyl and rubidium carbonate, ethyl acetate is distilled to recover, obtains 2,5 furans
It mutters diformazan acid dialkyl ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 91%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole tetrafluoro boric acid of ionic liquid 1- ethyl diethyldithiocarbamate ether according to
The present embodiment the method is reused 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester according to the present embodiment the method,
The conversion ratio of furfural is 100%, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 91%.
Embodiment 5
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 2g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
1MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 2.8 that filtrate, which is acidified to pH with sulfuric acid, suction strainer,
Washing dries 4h at 80 DEG C to get furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 2g cesium carbonate, -3 methylimidazole hexafluorophosphoric acid of 150g ionic liquid 1- ethyl diethyldithiocarbamate ether, 11ml second
Alcohol is sequentially introduced into autoclave, closed, and nitrogen purges 3 times, filling CO 2 to 3MPa, and reaction temperature is 120 DEG C, instead
It is 8h between seasonable, 100ml ethyl acetate is added after completion of the reaction, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether
In, filtering is recovered to -3 methylimidazole hexafluorophosphate cesium carbonate of 1- ethyl diethyldithiocarbamate ether, ethyl acetate is distilled to recover, is obtained
2,5- furandicarboxylic acid dialkyl ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole hexafluorophosphoric acid of ionic liquid 1- ethyl diethyldithiocarbamate ether according to
The present embodiment the method is reused 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester according to the present embodiment the method,
The conversion ratio of furfural is 100%, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
Embodiment 6
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 2g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
1MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 2.8 that filtrate, which is acidified to pH with sulfuric acid, suction strainer,
4h is dried in washing at 80 DEG C, both obtains furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 2g cesium carbonate, -3 methylimidazole hexafluorophosphoric acid of 150g ionic liquid 1- ethyl-methyl ether, 11ml second
Alcohol is sequentially introduced into autoclave, closed, and nitrogen purges 3 times, filling CO 2 to 1MPa, and reaction temperature is 120 DEG C, instead
It is 8h between seasonable, 100ml ethyl acetate is added after completion of the reaction, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether
In, filtering is recovered to -3 methylimidazole hexafluorophosphoric acid of 1- ethyl-methyl ether and cesium carbonate, ethyl acetate is distilled to recover, is obtained
2,5- furandicarboxylic acid dialkyl ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 97%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole hexafluorophosphoric acid of ionic liquid 1- ethyl-methyl ether according to
The present embodiment the method is reused 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester according to the present embodiment the method,
The conversion ratio of furfural is 100%, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 97%.
Embodiment 7
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 2g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
1MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 2.8 that filtrate, which is acidified to pH with sulfuric acid, suction strainer,
3h is dried in washing at 100 DEG C, both obtains furancarboxylic acid；
B. 2,5 furandicarboxylic acid dialkyl esters are synthesized:
By 10g furancarboxylic acid, 2g cesium carbonate, -3 methylimidazole tetrafluoro boric acid of 150g ionic liquid 1- nitrile methyl, 11ml ethyl alcohol according to
Secondary to be introduced into autoclave, closed, nitrogen purges 3 times, filling CO 2 to 3MPa, and reaction temperature is 120 DEG C, when reaction
Between be 8h, after completion of the reaction be added 100ml ethyl acetate, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether,
Filtering, is recovered to -3 methylimidazole tetrafluoro boric acid of 1- nitrile methyl and cesium carbonate, ethyl acetate is distilled to recover, 2,5- furans is obtained
Diformazan acid dialkyl ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole tetrafluoro boric acid of ionic liquid 1- nitrile methyl according to this reality
It applies the method to reuse 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester, furfural according to the present embodiment the method
Conversion ratio be 100%, the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
Embodiment 8
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 2g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
1MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 2.8 that filtrate, which is acidified to pH with sulfuric acid, suction strainer,
Washing dries 4h at 80 DEG C to get furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 3g cesium carbonate, -3 methylimidazole hexafluorophosphoric acid of 150g ionic liquid 1- nitrile methyl, 11ml ethyl alcohol according to
Secondary to be introduced into autoclave, closed, nitrogen purges 3 times, filling CO 2 to 3MPa, and reaction temperature is 120 DEG C, when reaction
Between be 8h, after completion of the reaction be added 100ml ethyl acetate, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether,
Filtering, is recovered to -3 methylimidazole hexafluorophosphoric acid of 1- nitrile methyl and cesium carbonate, ethyl acetate is distilled to recover, 2,5- furans is obtained
Diformazan acid dialkyl ester.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole hexafluorophosphoric acid of ionic liquid 1- nitrile methyl according to this reality
It applies the method to reuse 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester, furfural according to the present embodiment the method
Conversion ratio be 100%, the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
Embodiment 9
The preparation method of 2,5-furandicarboxylic acid dialkyl ester, the specific steps are as follows:
A. catalysis oxidation furfural is to furancarboxylic acid:
10g furfural and 2g copper oxide are sequentially introduced into autoclave, it is closed, nitrogen purge 3 times, be oxygenated to
1MPa, reaction temperature are 60 DEG C, reaction time 6h, Filtration of catalyst, and it is 2.8 that filtrate, which is acidified to pH with sulfuric acid, suction strainer,
4h is dried in washing at 80 DEG C, both obtains furancarboxylic acid；
B. 2,5- furandicarboxylic acid dialkyl ester is synthesized:
By 10g furancarboxylic acid, 2g cesium carbonate, -3 methylimidazole nitric acid of 150g ionic liquid 1- nitrile methyl, 11ml ethyl alcohol successively draws
Enter into autoclave, closed, nitrogen purges 3 times, filling CO 2 to 3MPa, and reaction temperature is 120 DEG C, and the reaction time is
100ml ethyl acetate is added after completion of the reaction, 2,5-furandicarboxylic acid dialkyl ester is extracted into anhydrous ether by 8h, filters,
It is recovered to -3 methylimidazole nitric acid of 1- nitrile methyl and cesium carbonate, ethyl acetate is distilled to recover, 2,5-furandicarboxylic acid two is obtained
Arrcostab.
The conversion ratio of furfural is 100% in the present embodiment, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
By the copper oxide catalyst of the present embodiment and -3 methylimidazole nitric acid of ionic liquid 1- nitrile methyl according to the present embodiment
The method is reused 10 times, prepares 2,5-furandicarboxylic acid dialkyl ester according to the present embodiment the method, furfural turns
Rate is 100%, and the yield of 2,5-furandicarboxylic acid dialkyl ester is 96%.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (10)
- The preparation method of 1.2,5- furandicarboxylic acid dialkyl esters, which comprises the following steps:It A. is furancarboxylic acid by furfuraldehyde through catalytic oxidation using copper oxide as catalyst；B. it synthesizes 2,5- furandicarboxylic acid dialkyl ester: furancarboxylic acid, carbonate, ionic liquid and alcohol is sequentially introduced into reaction under high pressure Closed in kettle, nitrogen purges 3 times, is filled with carbon dioxide to 1-4MPa, reaction temperature is 100-150 DEG C, reaction time 6- 24h；The ionic liquid is -3 methylimidazole tetrafluoro boric acid of 1- butyl, -3 methylimidazole hexafluorophosphoric acid of 1- butyl, 1- butyl -3 Methylimidazole nitric acid, -3 methylimidazole tetrafluoro boric acid of 1- ethyl diethyldithiocarbamate ether, -3 methylimidazole hexafluorophosphoric acid of 1- ethyl diethyldithiocarbamate ether, 1- - 3 methylimidazole hexafluorophosphoric acid of ethyl-methyl ether, -3 methylimidazole tetrafluoro boric acid of 1- nitrile propyl, -3 methylimidazole six of 1- nitrile propyl - 3 methylimidazole nitric acid of fluorophosphoric acid or 1- nitrile propyl.
- 2. preparation method according to claim 1, which is characterized in that the mass ratio of the copper oxide and furfural is 0.1:1- 0.3:1。
- 3. preparation method according to claim 1 or 2, which is characterized in that in step A, the reaction item of the catalysis oxidation Part are as follows: nitrogen purges 3 times, fills air or oxygen to 0.1-3MPa, reaction temperature is 30-60 DEG C, reaction time 4-6h.
- 4. preparation method according to claim 1,2 or 3, which is characterized in that the carbonate be sodium carbonate, potassium carbonate, Cesium carbonate or rubidium carbonate.
- 5. preparation method according to claim 1,2,3 or 4, which is characterized in that the mass ratio of the carbonate and furancarboxylic acid For 0.1:1-0.3:1.
- 6. according to claim 1, preparation method described in 2,3,4 or 5, which is characterized in that the matter of the ionic liquid and furancarboxylic acid Amount is than being 10:1-20:1.
- 7. according to claim 1, preparation method described in 2,3,4,5 or 6, which is characterized in that the alcohol is methanol, ethyl alcohol, third Alcohol or butanol.
- 8. preparation method according to claim 1,2,3,4,5,6 or 7, which is characterized in that mole of the alcohol and furancarboxylic acid Than for 2:1-10:1.
- 9. according to claim 1, preparation method described in 2,3,4,5,6,7 or 8, which comprises the following steps:A. catalysis oxidation furfural is furancarboxylic acid:Furfural and copper oxide are sequentially introduced into autoclave, closed, nitrogen purges 3 times, fills air or oxygen to 0.1- 3MPa, reaction temperature are 30-60 DEG C, reaction time 4-6h, and Filtration of catalyst, acidification of filtrate to pH is 3-2.5, are inhaled Filter, washing, drying, drying temperature are 80-120 DEG C, drying time 2-4h；The catalyst is 0.1 to the mass ratio of furfural: 1-0.3:1；B. 2,5 furandicarboxylic acid dialkyl esters are synthesizedFurancarboxylic acid, carbonate, ionic liquid and alcohol are sequentially introduced into autoclave, closed, nitrogen purges 3 times, fills dioxy Change carbon to 1-4MPa, reaction temperature is 100-150 DEG C, and organic solvent is added in reaction time 6-12h after completion of the reaction, filtering, Ionic liquid and catalyst are recycled, organic solvent is distilled to recover to obtain 2,5 furandicarboxylic acid dialkyl esters；Used alcohol is Methanol, ethyl alcohol, propyl alcohol or butanol；The carbonate is sodium carbonate, potassium carbonate, cesium carbonate or rubidium carbonate；The ionic liquid is - 3 methyl imidazolium tetrafluoroborate of 1- butyl, -3 methylimidazole hexafluorophosphate of 1- butyl, -3 methylimidazole nitric acid of 1- butyl, 1- - 3 methylimidazole tetrafluoro boric acid of ethyl diethyldithiocarbamate ether, -3 methylimidazole hexafluorophosphoric acid of 1- ethyl diethyldithiocarbamate ether, -3 first of 1- ethyl-methyl ether Base imidazoles hexafluorophosphoric acid, -3 methylimidazole tetrafluoro boric acid of 1- nitrile propyl, -3 methylimidazole hexafluorophosphoric acid of 1- nitrile propyl or 1- nitrile third The mass ratio of -3 methylimidazole nitric acid of base, the carbonate and furancarboxylic acid is 0.1:1-0.3:1, and the molar ratio of alcohol and furancarboxylic acid is 2:1- The mass ratio of 10:1, ionic liquid and furfural is 10:1-20:1.
- 10. preparation method according to claim 9, which is characterized in that the organic solvent is ethyl acetate or ether.
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